JPH106404A - Manufacture of optical three dimensional shaped article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain excellent thermal physical properties, mechanical properties, and mechanical workability by a method wherein a specific photo-setting liquid is used, an optical cured laminate having a specific glass transition temperature is formed, and the laminate is post cured at a temperature higher by a specific temperature than the glass transition temperature. SOLUTION: A photo-setting liquid is used, and an optically cured laminate having a glass transition temperature of 70 to 120 deg.C is formed. Thereafter, it is post cured at a temperature higher by 30 to 100 deg.C than the glass transition temperature. The photo-setting liquid is a polymerizable mixture composed of (meth)acryloyl modified urethane containing methacryloyl modified urethane having at least a methacryloyl group as a radical polymerizable group in a molecule or methacryloyl and acryloyl modified urethane, and a radical polymerizable diluent capable of being polymerized with the (meth)acryloyl modified urethane. Further, the (meth)acryloyl modified urethane contains the radical polymerizable group by a 0.25 to 0.40mol unit per its 100g.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing an optical three-dimensional object. In the presence of a photopolymerization initiator, a layer of a photocurable liquid is formed, and at least a portion thereof is photocured by irradiating this layer with actinic radiation, for example, ultraviolet laser light, and then the photocured A new layer of the photo-curable liquid is formed on the layer, and the layer is irradiated with actinic radiation again to repeatedly photo-cur at least a portion of the layer. The formation of an optical three-dimensional object, which is an integrated photo-cured product, has been carried out (JP-A-62-2596).
6, JP-A-62-101408, JP-A-3-2143
2, European Patent Publication 250121). Such an optical three-dimensional structure is mainly used as a shape confirmation model. The present invention relates to a method capable of obtaining an optical three-dimensional structure having excellent shape characteristics and workability when hot as characteristics that can be used not only as a shape confirmation model but also as a practical part.

[0002]

2. Description of the Related Art Conventionally, when an optical three-dimensional object is manufactured using a photocurable liquid, an operation of irradiating a layer of the photocurable liquid with actinic radiation in the presence of a photopolymerization initiator as described above. After obtaining a photocured laminate in the green state by repeating the above, for the purpose of improving the physical properties of the laminate, the laminate is further post-cured by irradiation with actinic radiation, heat treatment, or the like. . However, there is a problem that the optical three-dimensional structure obtained in this manner is easily deformed in a hot state, for example, under a use condition of 110 ° C. or more, and has poor shape characteristics. The reason for this is that the resulting optical three-dimensional structure is largely due to lack of elastic properties such as rigidity when hot. By the way, in the technical field of producing a cured product by heat-curing a thermosetting resin such as a (meth) acryloyl polyester resin or an epoxy resin, generally, the thermal properties of the obtained cured product, for example, the elastic properties when hot, As means for improvement, 1) a method of using a curable resin having a high concentration of a polymerizable group for the purpose of increasing the crosslink density of the obtained cured product; Method to introduce rigid atomic groups such as ring-aromatic ring or aromatic imide bond, or to introduce rigid structure such as ladder structure or strong intermolecular alignment structure. 3) Thermosetting resin contains reinforcing fiber There is a method of causing the same. In a thermosetting resin using such technical means, a cured product obtained by heating and curing can have a glass transition temperature of 150 ° C. or more relatively easily. However, in a method of manufacturing an optical three-dimensional object by photocuring a layer of a photocurable liquid one by one to form a laminate thereof and post-curing the laminate, the above-described thermal Even if the physical property improving means is applied, there is a problem that not only the thermal physical properties, for example, the elastic properties at the time of hot working are not so much improved, but also the mechanical physical properties at room temperature are remarkably reduced. If the obtained optical three-dimensional structure is subjected to machining or assembly such as drilling or bolt assembly, cracks are likely to occur. Even if the above-mentioned means for improving physical properties are applied, the reason why the obtained optical three-dimensional molded article cannot sufficiently exhibit thermal properties and mechanical properties is not clear, but the progress of radical polymerization in both production methods is not clear. This is presumed to be due to the difference between the systems used for photocuring the photocurable liquid and the system used for heat curing the thermosetting resin. In any case, simply applying a photocurable liquid based on the conventional concept for expressing thermal physical properties is excellent in hot elasticity properties, and therefore excellent in hot hot shape properties, and at the same time, processability. An excellent optical three-dimensional object cannot be obtained.

[0003]

The problem to be solved by the present invention is that the conventional method for producing an optical three-dimensional object is
Also, even when applying the thermal property improving means employed in the conventional thermosetting of the thermosetting resin to this, an optical three-dimensional structure having excellent shape characteristics at the time of hot working and also excellent in processability can be obtained. The point is that you cannot do that.

[0004]

Means for Solving the Problems Thus, the present inventors have
As a result of intensive studies to solve the above-described problems, a specific photocurable liquid is used to form a photocured laminate having a specific glass transition temperature, and the laminate is post-cured at a specific temperature. Has been found to be correct and suitable.

That is, according to the present invention, a photocurable liquid layer is formed in the presence of a photopolymerization initiator, and at least a part thereof is photocured by irradiating the layer with actinic radiation. A new layer of a photocurable liquid is formed on the cured product, and the operation of irradiating this layer with actinic radiation again to photocure at least a portion thereof is repeated to form a photocured laminate. In a method for producing an optical three-dimensional structure including a step and a step of post-curing the thus-photocured laminate, a photocured laminate having a glass transition temperature of 70 to 120 ° C using the following photocurable liquid: Forming a body, and post-curing the photocured laminate at a temperature 30 to 100 ° C. higher than its glass transition temperature. .

Photocurable liquid: A methacryloyl-modified urethane having at least a methacryloyl group as a radical polymerizable group in a molecule or a (meth) acryloyl-modified urethane containing a methacryloyl / acryloyl-modified urethane, and a (meth) acryloyl-modified urethane. A polymerizable mixture comprising a polymerizable radical polymerizable diluent, wherein the (meth) acryloyl-modified urethane has a radical polymerizable group in an amount of 0.25 to 0.
Polymerizable mixture containing at a concentration of 40 mole units

In the present invention, the (meth) acryloyl-modified urethane constituting the photocurable liquid is a methacryloyl-modified urethane having at least a methacryloyl group as a radical polymerizable group in a molecule or a methacryloyl-modified urethane.
(Meth) acryloyl-modified urethane containing acryloyl-modified urethane. Such (meth) acryloyl-modified urethanes include 1) a methacryloyl-modified urethane having only a methacryloyl group as a radical polymerizable group in a molecule, and 2) a methacryloyl- and a acryloyl group having a radical polymerizable group in a molecule.
Acryloyl-modified urethane, 3) a mixture of the above-mentioned 1) methacryloyl-modified urethane and 2) methacryloyl-acryloyl-modified urethane, 4) the above-mentioned 1) methacryloyl-modified urethane, 2) methacryloyl-acryloyl-modified urethane and / or 3) )) And a mixture of an acryloyl-modified urethane having only an acryloyl group as a radical polymerizable group in the molecule.

The (meth) acryloyl-modified urethane can be appropriately selected from known (meth) acryloyl-modified urethanes and used. For example, 1) 1 mol of an n-valent polyisocyanate and a polyol (meth) having one hydroxyl group in a molecule obtained by esterification of a polyol and (meth) acrylic acid
(Meth) obtained from nmol of acrylic acid partial ester (hereinafter referred to as (meth) acrylic ester monol)
Acryloyl-modified urethane (as described in JP-A-4-72353), 2) (meth) obtained from 1 mol of n-valent polyol, nmol of diisocyanate and nmol of the above (meth) acrylic ester monol Acryloyl-modified urethane (as described in JP-A-2-145616), 3) (meth) acryloyl-modified urethane obtained from 1 mol of n-valent polyol and n mol of isocyanatoalkyl (meth) acrylate -1
63116 and JP-A-6-199962) 4) 1 mol of a polyol (meth) acrylate having n free hydroxyl groups in a molecule and n mol of isocyanatoalkyl (meth) acrylate The resulting (meth) acryloyl-modified urethane (JP-A-4-53
809), and 5) the above (meth) acryloyl-modified urethane mixtures of 1) to 4).

In the present invention, the (meth) acryloyl-modified urethane has a radical polymerizable group of 0.25 to 0.1 per 100 g of the above-mentioned (meth) acryloyl-modified urethane.
Use those containing at a concentration of 40 mol units. As the (meth) acryloyl-modified urethane, a one-component (meth) acryloyl-modified urethane may be used.
A case where a (meth) acryloyl-modified urethane of a component system or more is used, the latter case is preferred,
Above all, a two-component (meth) acryloyl-modified urethane having different radical polymerizable group contents and a three-component (meth) acryloyl-modified urethane having different radical polymerizable groups are used. Is preferred. In particular, among such two-component (meth) acryloyl-modified urethanes, a (meth) acryloyl-modified urethane containing a radical polymerizable group at a concentration of 0.35 mol unit or more per 100 g of a (meth) acryloyl-modified urethane is preferably used. A mixture with (meth) acryloyl-modified urethane, which is contained in a concentration of 30 mol units or less, is preferable, and 100 g of (meth) acryloyl-modified urethane is preferable.
(Meth) acryloyl-modified urethane containing a radical polymerizable group at a concentration of 0.35 to 0.55 mol unit per unit and a concentration of 0.15 to 0.30 mol unit per unit (meth)
Mixtures with acryloyl-modified urethanes are more preferred.
Also, among the three-component (meth) acryloyl-modified urethanes, (meth) acryloyl-modified urethane containing a radical polymerizable group at a concentration of 0.45 to 0.65 mol unit per 100 g of (meth) acryloyl-modified urethane and 0% (Meta) at a concentration of .25 to 0.40 mol unit
A mixture of acryloyl-modified urethane and (meth) acryloyl-modified urethane, which is contained in a concentration of 0.10 to 0.20 mol unit, is preferred.

In the present invention, the concentration (in mol units) of a radical polymerizable group per 100 g of (meth) acryloyl-modified urethane is calculated by the following formula 1 when it is a one-component (meth) acryloyl-modified urethane. Value. In the case of a (meth) acryloyl-modified urethane of a two-component or more system,
The value calculated by the following formula 1 for the acryloyl-modified urethane is determined, and the calculated value is then used to calculate the weight ratio of each (meth) acryloyl-modified urethane in the total (meth) acryloyl-modified urethane ｛the total (meth) acryloyl The value obtained by multiplying the weight ratio の when the modified urethane is set to 1 is obtained, and the value obtained by multiplying the final value is the total value.

Formula 1: Concentration of radical polymerizable group (mol unit) = (n /
M) × 100 (in the formula 1, M: molecular weight of (meth) acryloyl-modified urethane n: number of polymerizable groups of (meth) acryloyl-modified urethane)

In the present invention, the adjustment of the concentration of the radical polymerizable group of the (meth) acryloyl-modified urethane to be used is carried out by:
For example, when it is a one-component (meth) acryloyl-modified urethane, the raw material to be used for the synthesis of the (meth) acryloyl-modified urethane can be appropriately selected. Specifically, the molecular weight and the number of isocyanate functional groups in the case of a polyisocyanate, the molecular weight and the number of hydroxy functional groups in the case of a polyol, and the number of (meth) acryloyl functional groups in the case of a polyol (meth) acrylate partial ester are appropriately determined. This is achieved by selecting and combining these ingredients.

In the present invention, as the above-mentioned (meth) acryloyl-modified urethane, those having 3 to 8 radical polymerizable groups in the molecule are usually used, and those having 3 to 6 radical polymerizable groups are advantageous. Applicable to According to the present invention, the (meth) acryloyl-modified urethane preferably has a radical polymerizable group having a ratio of methacryloyl group / acryloyl group = 1/3 to 3/1 (molar ratio), and 1/1 to 3/1. / (Molar ratio) is more preferable.

The preferred (meth) acryloyl-modified urethane as described above includes diisocyanate / triol monomethacrylate / monoacrylate = 1/2.
(Molar ratio), diisocyanate / triol monomethacrylate / monoacrylate / diol monomethacrylate = 1/1/1 (molar ratio), diol / diisocyanate / triol monomethacrylate / monoacrylate = 1/2/2 (Molar ratio) reactants,
Reaction product of triol / diisocyanate / triol monomethacrylate / monoacrylate = 1/3/3 (molar ratio), triol / diisocyanate / triol monomethacrylate / monoacrylate / diol monomethacrylate = 1/3/2/1 (molar ratio) Or 1/3 /
Reaction product of 1/2 (molar ratio), tetraol / diisocyanate / diol monomethacrylate / diol monoacrylate = 1/4/2/2 (molar ratio) or 1/4/3
/ 1 (molar ratio) and a reactant of tetraol / diisocyanate / triol monomethacrylate / monoacrylate / diol monomethacrylate = 1/4/2/2 (molar ratio). In this case, as the diol, ethylene glycol, propylene glycol,
1.4-butanediol, neopentyl glycol,
Dihydric alcohols such as 1,6-hexanediol, cyclohexanedimethanol, cyclohexenedimethanol, dicyclopentyldimethanol, and polyetherdiols such as ethylene oxide and propylene oxide adducts of these dihydric alcohols are advantageously used. Applicable. As the triol, trihydric alcohols such as glycerin and trimethylolpropane and polyether triols such as ethylene oxide and propylene oxide adducts of these trihydric alcohols can be advantageously used. Further, as the tetraol, pentaerythritol and polyethertetraol such as ethylene oxide or propylene oxide adduct of pentaerythritol can be advantageously applied. As the diisocyanate, known diisocyanates can be used, but aromatic diisocyanates such as tolylene diisocyanate, methylene-bis- (4-phenylisocyanate) and isophorone diisocyanate, and aliphatic / alicyclic diisocyanates can be advantageously used.

In the present invention, the photocurable liquid is a polymerizable mixture comprising the above-mentioned (meth) acryloyl-modified urethane and a radical polymerizable diluent copolymerizable with the (meth) acryloyl-modified urethane. In the present invention, the kind of the radical polymerizable diluent is not particularly limited, and a known vinyl monomer can be used as the radical polymerizable diluent. For example, 1) alkyl (meth) acrylates, alkanediol di (meth) acrylates, alkanetriol tri (meth)
Acrylates, polyoxyalkylene polyols (meth) acrylates such as poly (meth) acrylates, 2) N-vinyl cyclic amides such as N-vinylcaprolactam, N-vinylpyrrolidone, 3) N, N-dimethyl (Meth) acrylic acid tertiary amides such as (meth) acrylic acid amide and (meth) acrylic acid morpholide. Among these, a polyol poly (meth) acrylate obtained from a di- to tetravalent polyol and (meth) acrylic acid or a mixture of this with a (meth) acrylic acid tertiary amide can be advantageously used.

The polyols which form the above-mentioned polyol poly (meth) acrylate include divalent and tetravalent polyols which include 1) ethylene glycol, propylene glycol, 1.4-butanediol, neopentyl glycol, 1,6- An alkanediol having 2 to 6 carbon atoms, such as hexanediol; 2) an alicyclic hydrocarbon group having 6 to 12 carbon atoms, such as cyclohexanedimethanol, cyclohexenedimethanol, dicyclopentyldimethanol; 3) (poly) ester diols obtained by reacting these diols with aliphatic lactones having 4 to 6 carbon atoms or aliphatic oxycarboxylic acids; 4) 2,2-bis (hydroxyethoxyphenyl) Propane, 2,2-bis (hydroxydiethoxyphenyl) propane, bis (hydroxypropoxy) Diols such as alkoxylated bisphenols having 2 to 3 carbon atoms in the alkoxyl group, such as phenyl) methane and bis (hydroxydipropoxyphenyl) methane; 5) glycerin, trimethylolpropane, 5-methyl-1,2,2 4-heptanetriol,
Trihydric alcohols such as 1,2,6-hexanetriol,
6) (poly) ester triols obtained by reacting these trihydric alcohols with aliphatic lactones or aliphatic oxycarboxylic acids having 4 to 6 carbon atoms; 7) alkylenes having 2 to 3 carbon atoms with these trihydric alcohols A triol such as (poly) ether triol obtained by reacting an oxide; 8) an aliphatic tetrahydric alcohol such as pentaerythritol; 9) an aliphatic lactone or aliphatic oxy having 4 to 6 carbon atoms in the aliphatic tetrahydric alcohol. (Poly) ester tetraols obtained by reacting carboxylic acids; 10) Tetraols such as (poly) ethertetraols obtained by reacting aliphatic tetrahydric alcohols with alkylene oxides having 2 to 3 carbon atoms. .

In the present invention, the ratio of the radical polymerizable diluent in the photocurable liquid is not particularly limited.
The proportion is usually 30 to 70% by weight. In the present invention, a polymerizable mixture comprising the above (meth) acryloyl-modified urethane and a radical polymerizable diluent is used as a photocurable liquid. The (meth) acryloyl used in 100 g of the photocurable liquid is used. It is preferred that the radical polymerizable group based on the modified urethane be contained in a concentration of 0.12 to 0.22 mol unit. As described below, in a method of forming a photocured laminate using a photocurable liquid and further post-curing the laminate to produce an optical three-dimensional structure, a glass transition temperature of 70 to 120 ° C is used. This is because it is advantageous for forming a photo-cured laminate having such properties, and is advantageous for obtaining an optical three-dimensional structure having desired thermal and mechanical properties. The concentration of the radical polymerizable group based on the (meth) acryloyl-modified urethane as described above in the photocurable liquid can be adjusted by the use ratio of the radical polymerizable diluent used for preparing the photocurable liquid. it can.

In the present invention, in order to form a photocured laminate using the photocurable liquid described above, a known optical three-dimensional molding method using a direct drawing method of energy rays can be applied. In the present invention, in forming such a laminate, the thickness of one layer is not particularly limited, but is usually 1 mm or less,
Preferably it is 10 to 200 μm. In the present invention, a photocured laminate having a glass transition temperature of 70 to 120 ° C is formed. In the present invention, the glass transition temperature is the temperature at which the ratio of the loss elastic modulus to the storage elastic modulus, that is, the loss sine (Tan δ) shows the maximum value in the measurement of dynamic viscoelasticity (for example, by Yasutoshi Saito, Basics of Thermal Analysis for Material Science, Kyoritsu Publishing, 1990). To obtain a photocured laminate having such a glass transition temperature,
This is achieved by controlling the degree of curing of the photocurable liquid during photocuring. This includes, for example, (1) the curing properties of the photocurable liquid, (2) the irradiation energy per unit volume given to the photocurable liquid, and the like. It is determined by the thickness and the irradiation energy per unit area (exposure intensity), and the irradiation energy can be arbitrarily changed depending on the output of the active radiation, the scanning speed, the scanning line interval, and the like. In the present invention, these photocuring conditions are appropriately selected to form a photocured laminate having a desired glass transition temperature.

In the present invention, the photocured laminate is obtained as a so-called green shaped object obtained by repeatedly performing the above-described operation of forming a layer of the photocurable liquid and photocuring by irradiating the layer with actinic radiation. It is obtained. In the present invention, the glass transition temperature of the photocured laminate is set to 70 to 120 ° C, preferably 75 to 110 ° C. When the glass transition temperature of the photo-cured laminate is lower than 70 ° C., fine cracks are easily generated in an optical three-dimensional structure obtained by post-curing such a laminate, and mechanical properties are deteriorated. It will be. On the other hand, when the glass transition temperature of the photocured laminate exceeds 120 ° C., the optical three-dimensional structure obtained by post-curing such a laminate does not have excellent thermal and mechanical properties. The effect of improving physical properties by post-curing is small.

In the present invention, the photocured laminate having a specific glass transition temperature thus obtained is post-cured at a temperature 30 to 100 ° C. higher than the glass transition temperature.
It is preferred to post cure at temperatures as high as ~ 85 ° C. For the post-curing time, the present invention is not particularly limited,
Usually, it is 1 to 5 hours. According to the present invention, in the post-curing, the photo-cured laminate can be irradiated with actinic radiation to further photo-cur the surface thereof, and then thermally cured. In the method of the present invention, examples of the actinic radiation used for photocuring include visible light, ultraviolet light, and an electron beam.
Ultraviolet laser light can be advantageously applied.

[0020]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Preferred embodiments of the present invention include the following 1) to 8). 1) A solution prepared by dissolving 3 parts by weight of 1-hydroxycyclohexyl phenyl ketone as a photopolymerization initiator in 100 parts by weight of the following photocurable liquid (A-1) was used. A light-cured laminate having a glass transition temperature of 91 ° C. was scanned in one direction with an argon laser beam under the light-curing conditions of an upper scanning line interval of 0.05 mm, an exposure intensity of 22.4 mJ / cm ² , and an exposure depth of 0.30 mm. A method for producing an optical three-dimensional structure, comprising forming a body and post-curing the laminate at 150 ° C. for 2 hours. Photocurable liquid (A-1): (meth) acryloyl-modified urethane having a radical polymerizable group content of 0.46
30 parts by weight of methacryloyl / acryloyl-modified urethane (mol units / 100 g) and 30 parts by weight of methacryloyl / acryloyl-modified urethane having a radical polymerizable group content of 0.19 mol units / 100 g (meth) Using acryloyl-modified urethane (concentration of radically polymerizable group: 0.33 mol unit / 100 g), mixed with 20 parts by weight of dicyclopentyl dimethylene diacrylate and 20 parts by weight of acrylic acid morpholide as a radically polymerizable diluent Dissolved polymerizable mixture

2) A photo-cured laminate having a glass transition temperature of 82 ° C. was formed in the same manner as in the above 1) except that the exposure intensity was 18.0 mJ / cm ² and the exposure depth was 0.24 mm. And a method for producing an optical three-dimensional structure by post-curing the laminate at 150 ° C. for 2 hours.

3) The following photocurable liquid (A-2) was used, and the thickness of one layer was 0.10 mm and the exposure intensity was 10.2 mJ / c.
A photocured laminate having a glass transition temperature of 102 ° C. was formed in the same manner as in the above 1) except that m ² and the exposure depth were 0.15 mm.
A method for producing an optical three-dimensional object to be cured after an hour. Photocurable liquid (A-2): As a (meth) acryloyl-modified urethane, the content of the radical polymerizable group is 0.19.
30 parts by weight of a methacryloyl / acryloyl-modified urethane (mol unit / 100 g), 10 parts by weight of a methacryloyl / acryloyl-modified urethane having a radical polymerizable group content of 0.61 mole unit / 100 g, and a radical polymerizable group content of 0 part 3.39 mol / 100 g of methacryloyl / acryloyl-modified urethane 15 parts by weight
Using a component-based (meth) acryloyl-modified urethane (concentration of radically polymerizable group: 0.32 mol unit / 100
g) A polymerizable mixture obtained by mixing and dissolving 25 parts by weight of dicyclopentyl dimethylene diacrylate as a radical polymerizable diluent and 20 parts by weight of acrylic acid morpholide

4) The photocurable liquid (A-2) of the above 3) is used, and the exposure intensity is 8.8 mJ / cm ² and the exposure depth is 0.12 mm.
94 ° C. in the same manner as in 1) except that
A method for producing an optical three-dimensional structure, comprising: forming a photocured laminate having a glass transition temperature of; and post-curing the laminate at 150 ° C. for 2 hours.

5) The following photocurable liquid (A-3) was used, the thickness of one layer was 0.50 mm, and the exposure intensity was 67.6 mJ / c.
A photocured laminate having a glass transition temperature of 111 ° C. was formed in the same manner as in 1) except that the m ² and the exposure depth were 0.75 mm.
A method for producing an optical three-dimensional object to be cured after an hour. Photocurable liquid (A-3): (meth) acryloyl-modified urethane having a radical polymerizable group content of 0.33
A one-component (meth) acryloyl-modified urethane consisting of 60 parts by weight of methacryloyl-acryloyl-modified urethane (mol unit / 100 g) was used, and 20 parts by weight of dicyclopentyl dimethylene diacrylate as a radical polymerizable diluent and morphol acrylate were used. Polymerizable mixture obtained by mixing and dissolving 20 parts by weight

6) The photocurable liquid (A-3) of the above 5) was used, and the exposure intensity was 50.2 mJ / cm ² and the exposure depth was 0.60.
except that the distance was set to 10 mm, as in 1) above.
A method for producing an optical three-dimensional structure, comprising forming a photocured laminate having a glass transition temperature of 5 ° C and post-curing the laminate at 150 ° C for 2 hours.

7) A glass transition temperature of 111 ° C. was obtained in the same manner as in 1) except that the following photocurable liquid (A-4) was used and the exposure intensity was 20.4 mJ / cm ^2. Having a photocured laminate having
A method for producing an optical three-dimensional object which is post-cured at 0 ° C. for 2 hours. Photocurable liquid (A-4): As a (meth) acryloyl-modified urethane, the content of the radical polymerizable group is 0.19.
Two-component (meth) obtained by mixing 40 parts by weight of methacryloyl / acryloyl-modified urethane (mol unit / 100 g) and 20 parts by weight of methacryloyl / acryloyl-modified urethane having a radical polymerizable group content of 0.61 mol unit / 100 g. Using acryloyl-modified urethane (concentration of radically polymerizable group: 0.33 mol unit / 100 g), mixed with 20 parts by weight of dicyclopentyl dimethylene diacrylate and 20 parts by weight of acrylic acid morpholide as a radically polymerizable diluent Dissolved polymerizable mixture

8) The photocurable liquid (A-4) of the above item 7) was used, and the exposure intensity was 14.1 mJ / cm ² and the exposure depth was 0.20.
except that the distance was set to 10 mm, as in 1) above.
A method for producing an optical three-dimensional structure, comprising forming a photocured laminate having a glass transition temperature of 0 ° C. and post-curing the laminate at 160 ° C. for 2 hours.

Hereinafter, the structure and effects of the present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to these examples. In the following Examples and Comparative Examples, “parts” means “parts by weight” and “%” means “% by weight”.

[0029]

【Example】

Test Category 1 (Preparation of Photocurable Liquid) According to the method described in JP-A-6-199962, methacryloyl / acryloyl-modified urethane U
-1 {Glycerin monomethacrylate / monoacrylate / tolylene diisocyanate / hydroxyethyl methacrylate 1 mol adduct of caprolactone = 1/1/1
(Molar ratio) and methacryloyl / acryloyl-modified urethane U-2 {polypropoxylated glycerin (average molecular weight 300) / tolylene diisocyanate / caprolactone 1 mol adduct of hydroxyethyl acrylate / 1 mol of caprolactone of hydroxyethyl methacrylate Adduct = reactant of 1/3/1/2 (molar ratio)
And were synthesized. 30 parts of the synthesized methacryloyl / acryloyl-modified urethane U-1, 30 parts of methacryloyl / acryloyl-modified urethane U-2, 20 parts of acrylic acid morpholide and 20 parts of dicyclopentyl dimethylene diacrylate were mixed and dissolved at room temperature, Photocurable liquid A-1 was prepared. Similarly, photocurable liquids A-2 to
A-4 and R-1 to R-6 were prepared. These contents are summarized in Table 1.

[0030]

[Table 1]

In Table 1, U-1: 1 mol of caprolactone adduct of glycerin monomethacrylate / monoacrylate / tolylene diisocyanate / hydroxyethyl methacrylate = 1/1 /
1 (molar ratio), wherein the concentration of the radical polymerizable group is 0.46 mol unit / 100 g, and a methacryloyl group / acryloyl group (hereinafter referred to as M / A) U-2: polypropoxylated glycerin (average molecular weight 30)
0) / tolylene diisocyanate / hydroxyl acrylate 1 mol adduct of caprolactone / hydroxyethyl methacrylate 1 mol adduct of caprolactone =
It is a reactant of 1/3/1/2 (molar ratio), the content of the radical polymerizable group is 0.19 mol unit / 100 g, and M / A = 2 / 1
(Molar ratio) U-3: glycerin monomethacrylate / monoacrylate / isophorone diisocyanate = 2/1 (molar ratio)
Wherein the content of the radically polymerizable group is 0.
61 mol units / 100 g, having M / A = 2/2 (molar ratio) as a radical polymerizable group in the molecule. U-4: cyclohexanedimethanol / isophorone diisocyanate / glycerin monomethacrylate monoacrylate = A 1/2/2 (molar ratio) reactant,
When the content of the radical polymerizable group is 0.39 mol unit / 10
0 g, and M / A = as a radical polymerizable group in the molecule.
Having a ratio of 2/2 (molar ratio) U-5: polypropoxylated glycerin (average molecular weight 30
0) / tolylene diisocyanate / glycerol monomethacrylate / monoacrylate / caprolactone 1 mol adduct of hydroxyethyl methacrylate = 1/3/2
/ 1 (molar ratio), the concentration of the radical polymerizable group is 0.33 mol unit / 100 g, and M / A = 3/2 (molar ratio) as a radical polymerizable group in the molecule. RU-5: polypropoxylated glycerin (average molecular weight 3
00) / tolylene diisocyanate / glycerol diacrylate / hydroxyethyl acrylate, 1 mol adduct of caprolactone = 1/3/2/1 (molar ratio) with a radical polymerizable group content of 0.34 Molar unit / 100 g, having only an acryloyl group as a radical polymerizable group in the molecule S-1: Dicyclopentyl dimethylene diacrylate S-2: Acrylic acid morpholide

Test Category 2 (Formation of a photo-cured laminate, production of an optical three-dimensional molded article, evaluation thereof, etc.) Example 1 A three-dimensional NC table equipped with a container and an argon laser beam (output: 400 mW, wavelength: 3510 and 3640 Angstrom) control system. 1 part of the photopolymerization initiator per 100 parts by weight of the photocurable liquid prepared in Test Category 1 in the above container
-A solution for molding in which 3 parts by weight of hydroxycyclohexyl phenyl ketone is dissolved is filled, and a horizontal surface (X-
A photocurable liquid is supplied to the Y-axis plane) at a thickness of 0.20 mm, and argon laser light focused from the direction perpendicular to the surface (XY-axis plane) (Z-axis direction) is subjected to three-dimensional CAD.
Scan based on the data entered in the following conditions,
A predetermined part was cured. The scanning conditions were one-way scanning in the Y-axis direction with a scanning line interval of 0.05 mm, an exposure intensity of 22.4 mJ / cm ² , and an exposure depth of 0.30 mm. A molding solution was newly supplied onto the cured product at a thickness of 0.20 mm, and was similarly cured. In the same manner, three laminates for measuring mechanical properties in which a total of 15 layers were laminated, one laminate for measuring thermal properties in which a total of 20 layers were laminated, and a laminate for measuring a glass transition temperature in which a total of five layers were laminated. One laminate for evaluating machinability was formed by laminating three and a total of 100 layers. After each of the photocured laminates was washed with isopropyl alcohol, the glass transition temperature of the laminate for measuring glass transition temperature was measured by the method described later and found to be 91 ° C. The post-curing temperature is set at 150 ° C. from the glass transition temperature, and the laminate for measuring mechanical properties, the laminate for measuring thermal properties, and the laminate for evaluating machinability are heated at 150 ° C. for 2 hours for post-curing. Then, an optical three-dimensional structure was manufactured. From these optical three-dimensional objects, a sample for measuring mechanical properties specified in JIS-K7113, a sample for measuring thermal properties specified in JIS-K7207, and a sample for evaluating machinability were obtained. Using these sample pieces, mechanical properties, thermal properties and machinability were measured or evaluated by the following methods. These results, including the glass transition temperature of the photocured laminate, are summarized in Table 2.

Examples 2 to 8 and Comparative Examples 1 to 14 As shown in Table 2, the type of the photocurable liquid, the supply thickness of the photocurable liquid of one layer, and the scanning conditions were changed to Example 1 In the same manner as in the above, a photocured laminate was obtained. The glass transition temperature of the obtained laminate for measuring glass transition temperature was measured by the following method. The laminate for mechanical property measurement, the laminate for thermal property measurement, and the laminate for machinability evaluation were post-cured in the same manner as in Example 1 at the temperature shown in Table 2,
An optical three-dimensional object was manufactured. From these optical three-dimensional objects, the same sample pieces for measuring mechanical properties, thermal property measurements, and sample pieces for evaluating machinability as in Example 1 were obtained. Using these sample pieces, mechanical properties, thermal properties and machinability were measured or evaluated. These results, including the glass transition temperature of the photocured laminate, are summarized in Table 2.

Measurement of glass transition temperature 55 mm × 10 mm from the laminated body for measuring glass transition temperature of each example.
A x2 mm sample piece was cut out. The dynamic viscoelasticity of this sample piece was measured, and a glass transition temperature (Tg) indicated by a peak temperature obtained from a Tan δ-temperature curve was obtained.
The results are shown in Table 2 as an average value of three test pieces.

Measurement of Mechanical Properties The three specimens for measuring mechanical properties in each example were subjected to JIS-
According to K7113, the tensile strength and the tensile modulus were measured at a tensile speed of 5 mm / sec. The results are shown in Table 2 as an average value of three test pieces.

Measurement of Thermal Properties The specimens for measuring thermal properties in each example are JIS-K720.
7, the heat distortion temperature (HDT) at a bending stress of 181.4 MPa was determined. The results are shown in Table 2.

Measurement of machinability Sample pieces for evaluation of machinability (30 mm × 100 mm × 2)
0mm) with a vise, and using a 10mmφ drill,
Drilling was performed under the conditions of a drill rotation speed of 600 rpm and a feed rate of 20 mm / min, and the machinability was evaluated based on the following criteria. The results are shown in Table 2. ：: No cracks or missing parts were generated at all △: Fine cracks were generated around the holes ×: Large cracks or missing parts were generated around the holes

[0038]

[Table 2]

In Table 2, * 1: Fine cracks occurred on the surface of the optically three-dimensional molded article

[0040]

As is apparent from the above description, the present invention described above has an object to produce an optical three-dimensional structure having excellent thermal and mechanical properties, and at the same time, excellent workability. There is an effect that can be.

──────────────────────────────────────────────────の Continuation of the front page (51) Int.Cl. ⁶ Identification code Agency reference number FI Technical display location B29L 9:00 (72) Inventor Koichi Matsueda 1-letter Niihama 6-letter, Niihama, Tahara-cho, Atsumi-gun, Aichi 119 (72) ) Inventor Junichi Tamura 3-2-1 Sakado, Takatsu-ku, Kawasaki-shi, Kanagawa Kanagawa Science Park Teijin Machinery Co., Ltd. Tokyo Research Center (72) Inventor Tsuneo Hagiwara 3-2-1 Sakado, Takatsu-ku, Kawasaki-shi, Kanagawa No. Kanagawa Science Park Tokyo Research Center, Teijin Machinery Co., Ltd.

Claims (6)

[Claims] 1. A photocurable liquid layer is formed in the presence of a photopolymerization initiator, and at least a part thereof is photocured by irradiating the layer with actinic radiation. Forming a new layer of photocurable liquid on top, forming a photocured laminate by repeating the operation of photocuring at least a portion of the layer by irradiating it with actinic radiation again, In the method for producing an optical three-dimensional structure including a step of post-curing the photocured laminate, using the following photocurable liquid,
Forming an optically cured laminate having a glass transition temperature of 70 to 120 ° C, and post-curing the photocured laminate at a temperature of 30 to 100 ° C above the glass transition temperature. A method for manufacturing three-dimensional objects. Photocurable liquid: (meth) acryloyl-modified urethane containing methacryloyl-modified urethane or methacryloyl / acryloyl-modified urethane having at least a methacryloyl group as a radical polymerizable group in the molecule, and copolymerizable with the (meth) acryloyl-modified urethane A polymerizable mixture comprising a radically polymerizable diluent, wherein said (meth) acryloyl-modified urethane is 100%
Polymerizable mixture containing a radical polymerizable group in a concentration of 0.25 to 0.40 mol unit per g 2. The method according to claim 1, wherein the (meth) acryloyl-modified urethane is
The method for producing an optical three-dimensional structure according to claim 1, wherein the radical polymerizable group has a methacryloyl group / acryloyl group in a ratio of 1/3 to 3/1 (molar ratio). 3. The photocurable liquid according to claim 1, wherein the photocurable liquid contains a radical polymerizable group based on (meth) acryloyl-modified urethane in a concentration of 0.12 to 0.22 mol unit per 100 g. A method for producing an optical three-dimensional object. 4. The (meth) acryloyl-modified urethane,
A (meth) acryloyl-modified urethane containing a radical polymerizable group in a concentration of 0.35 mol units or more per 100 g thereof and a (meth) acrylic-modified urethane containing a radical polymerizable group in a concentration of 0.30 mol units or less
The method for producing an optical three-dimensional structure according to claim 1, which is a two-component mixture with an acryloyl-modified urethane. 5. The (meth) acryloyl-modified urethane,
The amount of the radical polymerizable group is from 0.35 to 0.1 per 100 g.
The optical component according to claim 4, which is a two-component mixture of (meth) acryloyl-modified urethane contained at a concentration of 55 mol units and (meth) acryloyl-modified urethane contained at a concentration of 0.15 to 0.30 mol units. A method for manufacturing three-dimensional objects. 6. The (meth) acryloyl-modified urethane,
The radical polymerizable group is added in an amount of 0.45 to 0.1 per 100 g.
(Meth) acryloyl-modified urethane contained at a concentration of 65 mol units and (meth) acryloyl-modified urethane contained at a concentration of 0.25 to 0.40 mol units, and 0.10 to
3. A ternary mixture with a (meth) acryloyl-modified urethane contained in a concentration of 0.20 mol unit.
Or the manufacturing method of the optical three-dimensional molded item of 3.